Trimesonitriles

ABSTRACT

TRIMESONITRILES OF THE FORMULA   1,3,5-TRI(NC-),2-(((R)M,(X)N,(H)P-PHENYL)-NH-)BENZENE   WHERE R IS METHYL, ETHYL, TRIFLUOROMETHYL, METHOXY, NITRO, CYANO, AND HYDROXYL, X IS HALOGEN AND H IS HYDROGEN WITH M AND N VARYING FROM 0 TO 3, P FROM 0 TO 5 AND THE SUM OF M, N, AND P BEING 5 WITH THE PROVISO THAT WHEN METHYL AND CHLORO RADICALS ARE BOTH PRESENT, M IS 1 AND N IS 1 OR 2 AND WHEN METHYL AND NITO RADICALS ARE BOTH PRESENT, M IS 2 AND N IS 0. THE COMPOUNDS ARE ACTIVE FUNGICIDES, VIRICIDES, AND BARTERICIDES.

United Qtates 3,637,796 TRIMESONITRILES Robert D. Battershell,Painesville, Ohio, assignor to Diamond Shamrock Corporation, Cleveland,Ohio N Drawing. Filed Oct. 30, 1968, Ser. No. 772,052 Int. Cl. C07c121/64 US. Cl. 260-465 E 20 Claims ABSTRACT OF THE DISCLOSURETrimesonitriles of the formula 01 ON Rm I I I Xn NO N H 1 im where R ismethyl, ethyl, trifiuoromethyl, methoxy, nitro, cyano, and hydroxyl, Xis halogen and H is hydrogen with m and n varying from 0 to 3, p from 0to and the sum of m, n, and p being 5 with the proviso that when methyland chloro radicals are both present, m is 1 and n is 1 or 2 and whenmethyl and nitro radicals are both present, In is 2 and n is 0. Thecompounds are active fungicides, viricides, and bactericides.

SUMMARY OF THE INVENTION The present invention relates to compositionsof matter consisting of compounds having the structure:

01 ON m I I Xi, NO- N- H In (IJN where R is an alkyl, halogenated alkyl,alkoxy, nitro, cyano, amino or hydroxyl radical; X is halogen and H ishydrogen with m, n and p varying between 0 and 5 with the sum of m, nand p equal to 5.

The invention also relates to the preparation of such compounds from1,3,S-trichlorotrimesonitrile corresponding to the formula:

and a precursor corresponding to the formula:

wherein R is an alkyl, halogenated alkyl, nitro, cyano, alkoxy, amino orhydroxy radical; X is halogen and H is hydrogen with m, n and p varyingbetween 0 and 5 with the sum of m, n and p equal to 5.

The invention further relates to biologically-active compositionscontaining the compounds disclosed herein and further relates to methodsof killing pests by contacting said pests with a pesticidal amount ofsaid compound.

As used herein the terms pesticides," pesticidal and killing pests areemployed for convenience to refer to the killiing and/ or controlling ofat least one growth such as undesirable fungus, virus or bacteria andthus pesticidal compositions can include compositions which are commonlyknown as bactericides, viricides, fungicides and the like.

w I 3,637,796 1 Patented Jan. 25, 1972 DESCRIPTION OF THE PREFERREDEMBODIMENTS This invention presents compositions of substitutedtrimesonitriles of the general formula:

or ON Rm 1 1 Xn NC- N H in N D 2,4-diehloro-6-(anllino)-trimesonltri1e01 ON I I I I I 01 ON 2,4-di'chloro'6-(o-chloroanillno)-trlmesonitrileC1 CN 01 I 1'1 NC- -N 2,4-dichloro-G-(p-bromoanilino)-trimesonltrlle I II I I I 01 ON 2,tdichloro-fi-(p-hydroxyanillno)-trimesonltrlle N O N 0 HI O1 ON 2,4-dichloro4i-(p-aminoanillno)-trimesonitrile2,4-dichloro-6-(2, i-dimethylani1ino)-trlmesonltrile O1 ON OH:

I I Cl ON 2,4-dichloro-6-(3,4-dimethoxyanilino)-trimesonitrile 01 ON OOHZA-dichloro-fi-(o-bromoanilino)-trin1esonitrile OCH Cl ON Br I r I r ICl CN 2,4-dichloro-6-(2,3-dlmethylanllino)-trlmesonltrlle 01 CN CH; CH:

I I Cl CN ZA-dichloro-fi-(2,3-dich1oroanilino)-trimesonitrile 01 GN ClCl Cw-Q 2,4-dichloro-6-(o-hydroxyoanilino)-trimesonitrllo Cl CN I 01 (SN2,4-dichloto-6-(m-chloroanilino)-trimesonitrile Cl CN 012,4-diehloro-6-(p-chloroanilino)-trlmesonitrile2,4-dichloro-6-(2,4-d1fiuoroanilino)-trimesonltrlle Cl CN F I N- F I ClJN 2,4-dichloro-6-(o-ethylaniline)-trimesonitrlle vC 2H52,4-dlch1oro-6-(3-chloro-2-mothylanllino)-trlmesonltrlle2,4-dichlro-6-(3,4-dichloroanillno)-trimesonitrile C1 ON 01 2,4-dichloro 6'- (IQ-i0 dou-nilino) -trimes0niti'ile Cl CN I I I IiI I 3- Cl CNI2,-1-dichlor0-6- 02 ,4,5 trimetl1ylanilin0) trimcsonlltrile Cl CN I IIII I Cl CN CH \2,4-dichlor0-6-(2-chlor0 4,5-dimethylunilino)-tri1nesoni trile 2,4-dichl0r0-6- 2-eyan oa'nilino-trimesonit rile Cl ON CN I I Ell I I C1 CN While it is possible toapply the compounds in undiluted form to the plant or other material tobe protected, it is frequently desirable to apply them in admixture witheither solid or liquid inert adjuvants. Thus, they can be applied to theplants for fungicidal purposes, for example, by spraying the plants withaqueous or organic solvent dispersions of the compound. Similarly, woodsurfaces can be protected by applying a protective film of the compoundby brushing, spraying or dipping utilizing a liquid dispersion thereof.The choice of an appropriate solvent is determined largely by theconcentration of active ingredient which it is desired to employ, by thevolatility required in a solvent, the cost of the solvent and the natureof the material being treated. Among the many suitable organic solventswhich can be employed as carriers for the present pesticides, there maybe mentioned hydrocarbons such as benzene, toluene, xylene, kerosene,diesel oil, fuel oil and petroleum naphtha; ketones such as acetone,methyl ethyl ketone and cyclohexanone; chlorinated hydrocarbons such ascarbon tetrachloride, chloroform, trichloroethylene andperchloroethylene; esters such as ethyl acetate, amyl acetate and butylacetate; the monoalkyl ethers of ethylene and diethylene glycol, e.g.,the monomethyl or monoethyl ethers; alcohols such as ethanol,isopropanol and amyl alcohol; and the like.

The pesticidal compounds can also be applied to plants and othermaterials along with inert solid adjuvants or carriers such as talc,pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheatflour, soybean flour, pumice, tripoli, Wood flour, walnut shell flourand lignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agentsare advantageously employed in both the solid and liquid compositions.The surface active agent can be anionic, cationic or nonionic incharacter.

Typical classes of surface active agents include alkyl sulfonates,alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates, alkylarylpolyether alcohols, fatty acid esters,

of polyhydric alcohols, ethylene oxide addition products of such esters,addition products of long chain mercaptans and ethylene oxide, sodiumalkyl benzene sulfonates hav ing 14 to 18 carbon atoms,alkylphenolethylene oxides, e.g., p-isooctylphenol condensed with 10ethylene oxide units; and soaps, e.g., sodium stearate and sodiumoleate.

The solid and liquid formulations can be prepared by any suitablemethod. Thus, the active ingredients, in finely divided form if a solid,may be tumbled together with finely divided solid carrier.Alternatively, the active ingredient in liquid form, includingsolutions, dispersions, emulsions and suspensions thereof, may beadmixed with the finely divided solid carrier in amounts small enough topreserve the free-flowing property of the final dust composition.

When solid compositions are employed, in order to obtain a high degreeof coverage with a minimum dosage of the formulation, it is desirablethat the formulation be in finely divided form. The dust containing anactive compound as described above usually should be sufficiently finethat substantially all will pass through a 20-mesh Tyler.

sieve. A dust which passes through a ZOO-mesh Tyler sieve also issatisfactory.

For dusting purposes, preferably formulations are employed in which theactive ingredient is present in an amount of to of the total by weight.However,

concentrations outside this range are operative and compositionscontaining from 1 to 99% of active ingredient by weight arecontemplated, the remainder being carrier and/or any other additive oradjuvant material which EXAMPLE 1 Preparation of2,4-dichloro-6-(2-chloroanilino)- trimesonitrile To a solution of 6.45grams (0.025 mol) of trichlorotrimesonitrile in dimethyl sulfoxide atroom temperature was added a solution of 7.05 grams (0.055 mol) ofochloroaniline in dimethyl sulfoxide. After all of the aniline wasadded, the reaction mixture was stirred for 3 hours at around 70 C. Atthis time analysis of the reaction mixture by thin layer chromatographyshowed the reaction to be complete. The mixture was diluted with about 3volumes H O causing a yellow precipitate to form. The resulting 5.3grams of crude product were recrystallized from 'benzene to give 4.3grams of product melting at 193.5 to 194.5 C. and having the followinganalysis:

Calculated (percent): C, 51.7; H, 1.4; Cl, 30.8; N, 16.1. 'Found(percent): C, 52.1, 52.3; H, 2.3, 1.9; CI, 30.6; N, 16.1.

EXAMPLES 2-9 Preparation of other substituted trimesonitriles Using theequipment and procedure described in Example 1, the reactants noted inthe following Table 1 are :rea'ctedsubstantially according to theteachings of Exmay be desired. It is often advantageous to add small a 11,

TABLE 1 Elemental analysis (percent) Melting Calculated Found ExampleReactants Product O.) C H 01 N C H 01 N 2 Triehlorotrimesonitrile and2,4-diehl0r0-fi-(2,4-dimethyl- 217-219 59.8 2.9 20.8 16.4 60.5 3.4 20.716.8

2,4-dimethylani1ine. anilino)-trimesonitrile.

3 Trichlorotrimesonltrile and 2,4-dichloro-6-(2-br0moanil1no)- 1965-197546.0 1.3 18.1 14.3 46.1 1.3 18.2 14.3

2-bromoaniline. trimesonitrile.

4 Trichlorotrimesonltrile and 2,4-dichloro-6-(2,3-dimethyl- 233-234 59.83.0 20.8 16.4 60.0 3.6 21.4 16.5

2,3-dimethylaniline. anillno)-trlmes0mtri1e.

5 "do 2, -dichl0r0-6-(2,3-diohloro- 211-214 47.2 1.1 37.1 14.7 46.7 1.836.8 13.8

anilino)trimesouitrile.

6 Trichlorotrimesonitrlle and. 2,4-dichloro-6-(Z-hydroxyanilino)- 250-L554.7 1.8 54.9 2.6 21.5

2-hydroxyaniline. trimesonitrile.

7 Triehlorotrimesonitrile and 2,4-dichloro-6-(2,4-difiuoro- 237-238 51.61.2 20.3 16.0 51.4 1.8 20.2 16,7

2,4-difluoroaniline. an1lino)-trlmesonitrile.

8 Triehlorotrimesonitn'le and 2,4-dich10ro-6-(2ethylanilino)- 190-19359.8 3.0 16.4 60.4 3.2 16.7

2-ethy1aniline. trimesonitrile.

9 Triehlorotrimesonitrile and 2,4-dich1oro6-(3-chloro-2-methyl- 217-22053.1 2.0 29.4 15.5 63.2 2,0 29,9 15.9

3-ch1oro-2methy1aniline. anillno -trimesonjtrile.

percentages of surface active agents, e.g., 0.5 to 1% of EXAMPLE 10 thetotal COIHPOSIUOII y Welght, Preparation of2,4-dichloro-6-(4-hydroxyanilino)- For spray application, the activeingredient may be trimesonitrile dissolved or dispersed in a liquidcarrier, such as water or other suitable liquid. The active ingredientcan be in the form of a solution, suspension, dispersion or emulsion inaqueous or nonaqueous medium. Desirably, 0.5 to 1.0% by weight of asurface active agent is included in the liquid composition.

For adjuvant purposes, any desired quantity of surface active agent maybe employed, such as up to 250% of the active ingredient by weight. Ifthe surface active agent is used only to impart wetting qualities, forexample, to the spray solution, as little as 0.05% by weight or less ofthe spray solution need be employed. The use of larger amounts ofsurface active agent is not based upon wetting properties but is afunction of the physiological behavior of the surface active agent.These considerations are particularly applicable in the case of thetreatment of plants. In liquid formulations the active ingredient oftenconstitutes not over by weight of the total and may be 10%, or even aslow as 0.01%.

The pesticidal compounds of the present invention can To a solution of12.9 grams (0.05 mol) of trichlorotrimesonitrile in acetone at roomtemperature Was added an acetone solution of 11.9 grams (0.11 mol) of4-hydroxyaniline. After all of the aniline had been added, the reactionmixture was stirred for 4 hours at room temperature. Analysis of thereaction mixture by thin layer chromatography showed the reaction to becomplete. The mixture was diluted with 3 volumes of H 0 causing a yellowprecipitate to form. The resulting 16.0 grams of crude product wererecrystallized from methanol to give 12.0 grams of. product melting at284 to 286 C. and having the following analysis:

Calculated (percent): C, 54.7; H, 1.8; Cl, 21.6. Found (percent): C,54.8; H, 3.1; C1, 20.5.

EXAMPLES 11-19 Preparation of other substituted trimesonitriles Usingthe equipment and procedure described in Example 10, the reactants notedin the following Table 2 are reacted substantially according to theteaching of Example 10.

TABLE 2 Elemental analysis (percent) Melting Calculated Found p nt1Example Reactants Product C.) C H 01 N C H 01 N 1. Trichllorotrimesonitrlle and 2,%-( llichl0ro-6-(anilino)-trimesoni- 241242 57.51.9 17.9 58.1 2. 8 17. 7

8111 1110. l! G. 12 Trichlorotrlmosonitrile and 4-2,4-dichloro-6-(Pbromoanillnm- 332-333 45.9 1.3 14.3 46.7 2.3 13.6

bromoaniline. trimcsonitnile. 13 Trlchlorotrlmcsonltrilo and 4-2,4-dichloro-6-(4-aminoanllino)- 450 55.0 2.0 21.6 21.4 55.5 2.6 21.921.1

phcnylenediamine. trlmesonitrile. 14 Trlchlorotrimcsonitrlle and 3,4-2,4diehlcro-6-(3,4-dimethoxy- 238-239 54.7 2.7 19.0 15.0 54.7 3.6 19.815. 0

dimethoxyaniline. anilino)-trimesonitrile. 15Tritlzlhlorotrliimesonltrile and 3 2,1;-diohloro6:l(3-chloroanilino)-226-227 51.8 1.5 30.6 16.1 51.8 1.8 30.6 15.6

0 0102111! no. 11111680111 n e. 16 Trlfillilorotrllmesonitrllc and 4-2,idichloroii g i-chloroanilino)- 310-311 51.8 1.4 30.6 16.1 52.2 1.630.3 15.9

C OI'OZ-Hl 1116. 1111105011 fl 9. 17 Tigilchlorotrlimesonitrile and 3-2,4t-dichlor(}6-3-fiuoroanilino)- 244-245 54. 4 1. 5 21. 4 16. 9 55.0 1. 7 21. 8 16, 9

uoroani ine. r meson tri e. 18 Triclilorotrimesonitrile and 3-2,4-dichloro-6-(3-trifluoromethyl- 263-265 50.4 1.3 18.6 14.7 51.0 1.418.7 14.7

trifluoromethylaniline. anilino)trimesonitrile. 19Trichlorotrlmesonitrile and 3,4 2,4-dichloro-6(3,4-dichloro- 250-25147.2 1.1 37.1 14.7 48.1 1.6 37.3 14. 7

dichloroaniline. anilino)-trimesonitrile.

1 Decomposcs.

20 D Percent disease control Osage EXAMPLE 2() Compound (p.p.m E. blightL. blight 2,4di hl 6- Foliage protectant and eradicant teststriesgiiitriigf cmomamlmo) 1 5i 3% 3g 32 85 97 The tomato foliagedisease test measures the ability of g g 95 the test compound to protecttomato foliage against infec- 6 77 tion by early blight fungusAlternaria solani (E11. and fig g gpa o)- 12 2 94 100 Mart.) Jones andGrout and the late blight fungus n es n 32 2% g; Phytophthora infestans(Mont) deBary. The method used 13 24 7 employs tomato plants, 5 to 7inches high which are 4 8 0 to 6 weeks old. Duplicate plants, one setfor each test i & e y 1g: 95 92 fungus, are sprayed with various dosagesof the test a g? 32 formulation at 40 lbs/sq. in. air pressure whilebeing 1g 22 79 rotated on a turntable in a hood. The center of the turn-9 64 table is 45 inches from the nozzle of the spray gun. The 35 .fig gfg, fi 1g: 99 100 test formulation containing the test compound, acetone,32 stock emulsifier solution and distilled water is applied at 1% 37 73concentrations up to 1000 p.p.m. of the test chemical. 13 58 Lowerconcentrations of toxicant are obtained by emliq gfic lo o o)- 6% 100100 ploying less toxicant and more water, thereby maintaining 40 i 33 g?the same concentration of acetone and emulsifier. i 5 33 After the spraydeposit is dry, treated plants and con- 2 s9 93 trols (sprayed withformulation less toxicant) are sprayed 1 24 77 while bein rotated on aturntable with a spore suspension 2,4-dichloro-S-(3,4-dichloroanilino)-1,000 100 100 g t '1 containing approximately 20,000 conidia of A. solamper "111650111 T1 256 80 87 ml., or 150,000 sporangia of P. infestansper ml. The atomizer used delivers 20 ml. in the 30-second exposureEXAMPLE 21 period. The plants are held in a saturated atmosphere for B act erici des 24 hours at 70 F. for early blight and 60 F. for late Iblight to permit spore germination and infection before Testfor'mulatlons are examlqegl for ablllty t0 111111131t removal to thegreenhouse. After 2 days from the start of the 3010111211 growth of w laamylovora (E.a.),

the test for early blight and 3 days for late blight, lesion counts aremade on the 3 uppermost fully expanded leaves. The data are converted topercent disease control based on the number of lesions obtained on thecontrol plants. Dosages and percent disease control are given in thefollowing table:

Percent disease control Xanthomonas phaseoli (X.p.), Staphylococcusaurcus (S.a.), and Escherechia coli (13.0.) at various concentrations.The basic test formulation contains 0.125 g. of the test chemical (or0.125 ml. of a liquid), 4.0 ml. acetone, 2.0 ml. stock emulsifiersolution (0.5% Triton X-l55 in water by volume) and 94.0 ml. distilledwater, the concentration of toxicant in this formulation being 1250parts per million. Lower concentrations of toxicant are obtained bydiluting the basic formulation with distilled water.

Two ml. of each formulation is dispensed into a test tube which is thenplaced into a water bath maintained at 44 C. From a stock preparation(also held at 44 C.), 8 ml. of 20-percent nutrient agar is added to thetest tube giving a 1.5 dilution or a final concentration of 250 p.p.m.chemical in the agar. The contents of the test tube are then thoroughlymixed, while still warm, with the aid of a Vortex type mixer andimmediately poured into a sterile polystyrene Petri dish x 15 mm.).After the agar in the plate is set, suspensions of each organism aresimultaneously streaked onto the surface of the agar. After the plate isinoculated, it is incubated 24 to 48 hours at 30 C., after which timeeach organism is rated visually for growth inhibition by the candidatechemical. Estimates of percent growth inhibition are relative to growthof streak colonies in control plates obtained during individual tests.Using this procedure, the following results are obtained:

10 cating plant kill. Using this procedure, the following results areobtained:

Concen- Percent control Percent tration Dosage, disease Compound(p.p.m.) E.a. X.p. S.a. E.c. Compound tested lbs/acre control24-dichloro-6-(o-chloro- 8 100 50 100 100 2,4-dichloro-6(3-trifluoro-methylanilino)- anilino) -tri.mesonitr1le. 4 100 50 100 100trimesouitrile 64 100 2 100 50 100 1002,4-dichloro-6(2,3-dimethyl-ani1ino)- 1 50 50 50 50 trimesonitrile 64100 2,4-dich1oro-6-(p-hydroxy- 64 100 100 100 100 10anilino)-trimesonitrile. 32 100 100 100 100 EXAMP E 23 8 50 100 Viricidetest Zif ggmgg w- 3% Test formulations are examined for ability tocontrol 8 a host virus system, maize dwarf mosaic virus on Golden 4Bantam sweet corn. A test formulation containing 0.1 g. gm w m 250 .ofthe test chemical (or 0.1 ml. if a liquid), 4.0 ml.aceaI1111I10)-tI1meS0mm1etone, 2.0 ml. stock emulsifier solution (0.5%Triton 32 X-l55 in water by volume), and 94.0 ml. distilled Water 24dich1ow 6 (m ch1om 16 is prepared for both the soil drench and foilagespray anilino)-trimesonitrile. 8 treatments. The host virus system,maize dwarf mosaic 4 virus on Zea mays var. Golden X Bantam, is culturedin 2 4 dich1or .6.(o.hydroxy. 250 a four-inch clay pot. Virusinoculation is made by carboamllno)-tnmesommlerundum leaf abrasionmethod prior to treatment.

32 In the foliage spray application, 33 ml. of the test formu- 2'4dich10m 6 (0 bmm0 32 l atlon 1000 ppm.) are sprayed at pounds per squareanumomrimesonitmg 16 mch air pressure while the plants are being rotatedon a 8 turntable in a hood. Twenty-four hours after spraying, in2,4-dichloro-6-(o-ethy1- 32 the soil drench treatment, the testformulation is applied anilinw-trimesorlimleg at the soil surface ofeach pot; ml. of the formulation being equivalent to a dosage of thetest chemical of 64 ad lo g i -gzfl gggg pounds per acre. Effectivecontrol is determined through nl ril 4 visual observation of thepresence or absence of viral in- 24 dmm0m 6 (3 fiuom 250 fectionsymptoms ten days after inoculation. Using this 'anmno) mmesomtme 128procedure, the following results are obtalnedz 642,4-dichloro-tl-(2A-difiuoro- 21:2 Dosage Percent amhno)'tnmesommle' 8Compound Lbs/acre P.p.m. control 2,4 dich10ro 6 (23 djch1m.0 100 100 100100 2,4-dichloro-fi-(auilino)-trimesonit1ile 64: 1, 000 1002,4-d1chloro-6-(2,3-d1chloroan1l1no)- M1111) tnmesmmle' i igg 100trimesonitrileuu 64 1,000 100 8 50 502,4-d1chloro-6-(3,4-d1chloroa11ilino)- trirnesonitrile 64 1, 000 1002,4-dichloro-6-(3,4-dichloro- 250 Rusticide test This test determinesthe effective capacity of the test compound as systemic bean rusticides.The host-rust system employed is Uromyces phaseoli on Phaseolus vulgarisvar. Pinto which is tested in four-inch clay pots. A dosage of 45 ml. ofthe test formulation, equivalent to 45 mg. of chemical or 64 pounds peracre, is drenched on each pot. This test formulation contains 0.1g. (or0.1 ml. if a liquid) of the test chemical, 4.0 ml. acetone, 2.0 ml.stock emulsifier solution (0.5 Triton X-l in water by volume), and 94.0ml. distilled water. The concentration of toxicant in this formulationis 1000 parts per million. Lower concentrations of toxicant are obtainedby diluting the formulation with distilled water.

Twenty-four hours after application of the test chemical, the plants areinoculated by atomizing onto the plant leaves a single aqueoussuspension containing the ureidospore specie. Subsequently the plantsare kept for an overnight incubation period at F. and 100 percentrelative humidity. Pustule counts are made seven to ten days afterinoculation and effective control is reported as percent disease controlbased upon pustule development in nontreated control plants.Additionally, phytotoxicity of the plants by the test chemical is ratedby visual observation on a scale from 0, indicating no plant injury, to11, indi- EXAMPLE 24 Systemic bactericidal test Test formulations areexamined for ability to control tomato \crown gall (Pseudomonas phaseolicola). A test formulation containing 0.24 g. of the test chemical (or0.24 ml. if a liquid 4.0 ml. acetone, 2.0 ml. stock emulsifier solution(0.5% Triton X- in water by volume), 94.0 ml. distilled water isprepared for both the soil drench and foliage spray treatments.Individual tomato plants, var. Rutgers, are planted in 3M2-inch claypots and are 3 to 5 inches tall at treatment time. Stem punctureinoculation, at the cotylodonary node, with a cellular suspension of thePseudomonas phaseolicola is made one to two hours prior to the soildrench and foilage spray treatment.

In the soil drench treatment, the test formulation is applied at thesoil surface of each pot; 17.5 ml. of the formulation being equivalentto a dosage of the test chemical of 64 lbs. per acre. Control isdetermined through visual observation of tumor formation 10 to 14 daysafter treatment. Using this procedure, the following results areobtained:

It is to be understood that the invention is not limited by the specificexamples and embodiments described here- 1 1 inabove, but includes suchchanges and modifications as may be apparent to one skilled in the artupon reading the appended claims.

What is claimed is: 1. A composition of matter of the structural formula01 CN Rm r r Xn NC- N H 01 (EN where R is a methyl, ethyl,trifiuoromethyl, methoxy, nitro, cyano and hydroxyl group, X is achloro, bromo, fluoro and iodo group, and H is hydrogen with m and nbeing from to 3, p from 2 to 5, and the sum of m, n, and p being 5 withthe proviso that when methyl and chloro radicals are both present, m is1 and n is l or 2 and when methyl and nitro radicals are both present,In is 2 and n is O.

. 2,4-dichloro-6- (anilino -trimes onitrile.

. 2,4-dichloro-6- (o-chloroanilino -trimesonitrile.

. 2,4-dichloro-6- (p-bromoanilino -trimesonitrile.

. 2,4-dichloro-6-(p-hydroxyanilino)-trimesonitrile.

. 2,4-dichloro-6- (p-aminoanilino -trimesonitrile.

. 2,4-dichloro-6-(2,4-dimethylanilino)-trimesonitrile.

\IQUI-kO-IN 8. 2,4-dich10r0-6- 3 ,4-dimethoxyanilino -trimesonitrile. 9.2,4-dich1oro-6- (o-bromoanilino -trimesonitrile. '10. 2,4-dichloro-6-2,3-dimethylanilino -trimesonitrile. 11. 2,4-dich1oro- 6-2,3-dichloroanilino) -trimesonitrile. 12.2,4-dichlor0-6-(o-hydroxyanilino)-trimesonitrile. 13. 2,4-dichloro-6-(m-chloroanilino -trimesonitrile. 14. 2,4dich1oro-6-(3-chloro-2-methylanilino)-trimesonitrile.

. 2,4-dichloro-6- 3-fiuoroanilino -trimesonitrile.

. 2,4-dich1oro-6- (p-chloroanilino -trimesonitrile.

. 2,4-dichloro-6- (2,4-difiuoroanil-ino -trimesonitrile.

. 2,4-dichloro-6-(o-ethylanilino)-trimesonitrile.

. 2,4-dich1oro-6- 3-trifluoromethylanilino) -trimesoni-2,4-dichloro-6-(3,4-dichloroanilino)-trimesonitrile.

References Cited UNITED STATES PATENTS 2,200,343 5/1940 Ritter 260-465CHARLES B. PARKER, Primary Examiner C. F. WARREN, Assistant Examiner US.Cl. X.R.

UNTTED STATES PATENT OTTTQT CERTlFlCATE Cl CGRECllCN Patent No. 3 37,796Dated January 25, 1972 Invent Robert D. Battershell It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 2, lines 50-55, that portion of the formula reading --o1 m shouldread --NH2 Column 2, lines 55-60, that portion of the formula readingOCH should read CH Column 2, lines 67-72, that portion of the formulareading Br r should read Columns 7-8, Table 2, Example 12, under heading"Product", "2,4-dichloro-6-( t-bromoanilino)-trimesonitnile" should reed--2,4-dichloro-6-(4-bromoanilino)-trimesonitrile--.

Column 10, line 49, after "liquid insert Signed and sealed this 5th dayof September 1972..

(SEAL) Atte st:

EDWARD M.,FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents FORM FO-105O (10-69) USCOMM-DC 60376-P69 U.S. GOVERNMENTPRINTING OFFICE: i969 0-366-334

